Halogenated benzoyl glycollate ester compositions



v Patented Oct. 28, 1941 i- HALOGE [2.260.628 ,ATEDLBENZOYL GLYGOLLATE ESTER. COMPOSITIONS v Lucas P. Kyrides, Webster Groves, Mo;,: assign'or to Monsanto Chemical Company, .St. Louis, Mozgnfii a'corporation of Delaware j .No Drawing. implication v March 4, 193 7, I I;

V 5 Serial N0 128,987.

21 Claims. (01.266-476) f Thisinvention relates to a novel class of neu-. tral halogenated benzoic ester compositions. This application is a continuation-in-partof my co-pending applications, SerialNo. 618,305, filed June 20, 1932, and Serial No. 648,986, 'filedDe cember 27, 1932 which have issued respectively as United States Pa'tents 2,073,937 and 2,073,938.

The invention has as one of its objects the provision of a class of organic esters which are in are permanen'tlymonom'eri'c, non-resinifiable' and non-polyinerizable. In thisrespect they are distinguishable from the-vinyl typecester compositions which do polymerize and resinify. They have a plasticizing or softening action on phenolaldehyde resins, styrene resins, vinyl type resin-s,

urea-formaldehyde resins, etc.

The preferred compositions "contemplated by the presen-t'invention' are the mono and poly chloro benzoic acid esters, in which the carboxylic group is'esterified by the hydroxylgroup of an ester of glycollic'acid and its homologues.

The following example illustrates an embodiment of the present invention."

176.5 grams of sodium o-chlorobenzoate are suspended in55 -grams of 99% ethyl alcohol and refluxed with agitation with 55 grams of ethyl chloroacetate for approximately hours. The

reaction mixture is then washed with'walter and the oil layer finally separated. This oil layer containing the ester is purified in the known manner as by distillation.

The product, ortho chlorobenzoyl ethyl glycollate distills at 182-185 C'. under 15 mm. pressure and at 315 C. at atmospheric pressure. I

The reaction may be represented as follows:

COONa C1+C1CH2O O 0 02115 COOCHQGOOCQHE +NaC1 acids'such as chloropropionic acid or a chloro' butyric"5acid. Similarly, the meta and para chlorobenzoic acids, including isomeric mixtures thereof, may be substituted for the ortho compound.v In lieu of thefmono chlorobenzoic acids the di 'or' tri-chloro" compounds may be used. Similarly,in lieu'fofithe ethyl ester of chloroacetic. acidone maysubstitute the chloroa'cetic. acidesterof other alcohols including cresol, phenol, methyl, propyl; but'yl, 'amyl or benzyl alcohol as well as 'chloroac'etic esters of monoialkyl ethers of glycol such as the mono ethyl ether of ethylene glycol and the dialkyl ether of glycerol, etc.

The manner of using theproducts described hereinas plasticizers .OI softeners is fully set forth in my co-pending .ztpplications identified above to which reference is hereby made. In the instant application, the compounds specifically claimed are the mono and poly, chlorobenzoyl glycollateesters and homologues of the glycollic esters. These compounds may be represented by the structural formula:

""ciosmco- -o-a-co-onl I where'Rrepresents a divalent aliphatic hydrocarbon group and R1 represents a monovalent aryl' hydrocarbon group; in the case of phenolic esters andamonovalentalkyl group in the case of allphatic alcoholesters;

What 'claimfis: J The ethyl glycollate acid. I

g 2.1 Aneutral chlorobenzoateester, the carboxyl group "of which is esterifiedwith the hyidroxyl' ester of o-chlorobenzoic I group of a'glycollate es te n the carboxyl group of said 'gly'collate esterheing'esterified with a satu-' rated alkyl alcohol containing an ether linkage.

3. A neutral chlorobenzoate ester, the carboxyl group of which is esterified with the hydroxyl group of a glycolla'te ester, the carboxyl group of said glycollate ester being esterified with a saturated monoalkyl ether of a glycol.

4. A neutral ester of a. chlorobenzoic acid, the carboxyl group of which i's-esterified by the hydroxyl group of an aliphatic ester of a hdyroxy aliphatic acid selected from a group consisting of hydroxyacetic acid, hydroxypropioni acid and I hydroxybutyric acid, the aliphatic groups having no unsaturated linkages.

5. A neutral alkyl glycollate ester of a chloro- 1 benzoic acid, wherein said alkyl group satu rated. v e

6. A neutral ester of a chlorobenzoic acid, the carboxyl group of which is esterified by the hydroxyl group of a saturated alkyl ester of a ydroxy aliphatic acid selected from a group consisting of hydroxy-acetic acid, hydroxypropionic acid and hydroxybutyric acid.

7. A neutral ester of a chlorobenzoic acid, the carboxyl group of which is esterified by the hydroxyl group of a saturated aliphatic ester of glycollic acid.

8. An ester of the following formula:

where R represents a divalent saturated aliphatic hydrocarbon group and R1 represents a group selected from the monovalent aryL-monovalent saturated alkoxyalkyl and monovalent saturated alkyl hydrocarbon radicals.

9. A neutral ester of a chlorobenzoic acid, the

carboxyl group of which is esterified, by the hydroxyl group of an ester of a hydroxy aliphatic acid, said ester being selected from the group consisting of saturated alkyl saturated alkoxy a1- kyl and aryl esters.

10. A neutral ester of a chlorobenzoic acid, the carboxyl group of which is este'rified by the hydroxyl group of an ester of a hydroxy aliphatic acid, said ester being selected from the group consisting of saturated alkyl saturated alkoxy alkyl and aryl esters and said acid being selected from agroup consisting of hydroxy-acetic acid, hydroxypropionic acid and hydroxybutyric acid.

11. A neutral ester of a polychlorobenzoic acid, the carboxyl group of which is esterified by the hydroxyl group of an ester of a hydroxy aliphatic acid, said ester being selected from the group consisting of saturated alkyl saturated alkoxy alkyl and aryl esters.

12. The ethyl glycollate ester of a monochlorobenzoic acid.

13. A neutral ester of a chlorobenzoic acid, the, carboxyl group of which is esterified by the hydroxyl group of an ester. of hydroxyacetic acid, said ester being selected from the group consisting of saturated alkyl, saturated alkoxyalkyl and aryl esters.

14. A neutral ester of a chlorobenzoic acid, the carboxyl group of which is esterified by the hydroxyl group of an ester of hydroxybutyric acid, said ester being selected from the group consisting of saturated alkyl, saturated alkoxyalkyl and aryl esters.

15. A neutral ester of a polychlorobenzoic acid, the carboxyl group of which is esterified by the hydroxyl group of an ester of a hydroxy aliphatic acid, said ester being selected from the group consisting of saturated alkyl, saturated alkoxyalkyl and aryl esters and said acid being selected from a group consisting of hydroxyacetic acid, hydroxypropionic acid and hydroxybutyric acid. 1

16. A neutral ester of a polychlorobenzoic acid, the carboxyl group of which is 'es'terified by the hydroxy group of an ester of hydroxybutyric acid, said ester being selected from the group consisting of saturated alkyl, saturated alkoxy alkyl and aryl esters.

17 -An ester of the following formula where R represents a divalent saturated aliphatic hydrocarbon group selected from the group consisting of ethylene, propylene and methylene and R1 represents a group selected from the monovalent aryl, monovalent saturated alkoxyalkyl and monovalent saturated alkyl radicals.

18. An ester of the following formula where R represents a saturated methylene group and R1 represents a group selected from the monovalent aryl, monovalent saturated alkoxyalkyl and monovalent saturated alkyl radicals.

19. A neutral chlorobenzoate ester, the carboxyl group of Which is esterified with the hydroxyl group of 'an hydroxy acid selected from the group consisting of hydroxy-acetic acid, hydroxypropionic acid and hydroxybutyric acid, the carboxyl group of said hydroxy acid being esterified with a saturated alkyl alcohol containing an ether linkage. I v 20. A neutral chlorobenzoate ester, the carboxyl group of which is esterified with the hydroxyl group of hydroxyacetic acid, the carboxyl group of said hydroxyacetic acid being esterified with a saturated alkyl alcohol containing an ether linkage.

21. A neutral chlorobenzoate ester, the carboxyl group of which is esterified with the hydroxyl group of hydroxybutyric acid, the carboxyl group of said hydroxy-butyric acid being esterified with a saturated alkyl alcohol containing an ether linkage.

- LUCAS P. KYRIDES. 

